Hydroformylation with Integrated SILP Catalyst-Membrane Separation Reaction System

Jakob M. Marinkovica, Alex Weißb, Eduardo J. García-Suáreza, Marco Haumannb, Anders Riisagera, Rasmus Fehrmanna

a CentreforCatalysisandSustainableChemistry,DepartmentofChemistry,TechnicalUniversityofDenmark(DTU),Kgs. Lyngby,2800,DenmarkbLehrstuhl für Chemische Reaktionstechnik,Friedrich-Alexander-Universität (FAU),Erlangen,91058,Germany

Fig.11:Afirst-classconsortiumofninepartnersfromfiveEuropeancountriesmakeupROMEO'steam

ConclusionsIn summary, preliminary results indicate that ROMEO’s “two-in-one” reactor

concept has a great potential to be applied in the chemical industry. At this point,

the mechanical stability of the membrane needs to be improved. If this is

achieved, a reduction in emissions, energy consumption, space needs and costs in

the chemical industry are expected with this new reactor type.

Fig.9:Magneticresonanceimage(MRI)ofSILPimpregnatedceramicsupport

Fig.7:Gas-phasehydroformylationwithROMEOreactor(withoutmembrane)

Results

Fig.8:Gas-phasehydroformylationwithROMEOreactor(withmembrane– harmedduringoperation)

ROMEO: Reactor Optimization by Membrane Enhanced Operation

Drawback in SILP hydroformylationLong-term catalytic performance test (Fig. 3) of SILP catalyst on

hydroformylation of olefins exhibits decreasing activity due to the formation

of “heavies” by undesired condensation reactions (Fig. 4). This hampers both,

activity and selectivity and prevents the implementation of SILP in industry.

Hydroformylation as large volume processHydroformylation is one of the largest homogeneously catalyzed processes in

the chemical industry. Catalysis with supported ionic liquid phase (SILP)

catalyst systems (Fig. 1) has successfully been established over the last

decades as an industrially attractive approach conducting liquid- and gas-

phase reactions.1 Hydroformylation of olefins by syngas (Fig. 2) to produce

aldehydes is a highly important and frequently studied catalytic reaction.

Several SILP catalyst systems have demonstrated industrial potential.2

Fig.2:Metalcatalyzedhydroformylationofolefinsbysyngas

ThisprojecthasreceivedfundingfromtheEuropeanUnion’sHorizon2020researchandinnovationprogramme undergrantagreementNo680395

[1]S.Bhaduri,D.Mukesh.HomogeneousCatalysis:MechanismsandIndustrialApplications,2ndEdition.JohnWiley&Sons,2014.

[2]R.Franke,D.Selent,ArminBor̈ner.AppliedHydroformylation.ChemicalReviews,2012,112(11),pp5675–5732.

Fig.10:Variousceramicsupports

References

Acknowledgements

Homogeneous catalysis• High activities and selectivities• High mechanistic understanding• Defined catalyst structures

Heterogeneous catalysis• Easy catalyst immobilization• Easy product recovery• Usually simplified technical processes

Fig.1:SupportedIonicLiquidPhase(SILP)materialsbuildthebridgebetweenhomogeneousandheterogeneouscatalysis

Fig.6:ROMEO‘s partners along the value chain

Fig.5:ROMEO’sreactorcombinestwoessentialprocesssteps

ROMEO’s two-in-one reactor design

(Fig. 5) improves long-term stability by

avoiding aldol condensation. This is

achieved by a membrane coating

enabling continuous and selective (by-)

product separation from the reaction.

Fig.4:Possibleformationof“heavies”duringhydroformylation

n-is

ose

lect

ivity

/ %

Con

vers

ion

/ %

Fig.3:Long-termperformancetestofSILPmaterials